KR20210074449A - Method of manufacturing the linear electrochromic device - Google Patents

Abstract

According to the present invention, a method of manufacturing a linear electrochromic device relates to a plate shape electrochromic device, which includes a first substrate, a first electrode layer on the first substrate, a second electrode layer on the first electrode layer, an electrolyte layer interposed between the first electrode layer and the second electrode layer, and an electrochromic layer. A linear electrochromic structure pattern is formed by cutting the plate shape electrochromic device in a direction perpendicular to an upper surface of the first substrate, and a protective film covering at least a portion of the linear electrochromic structure pattern is formed. Therefore, an excellent linear electrochromic device can be manufactured through a simple manufacturing process.

Description

Method of manufacturing the linear electrochromic device

The present invention relates to a method for manufacturing a linear electrochromic device.

The electrochromic refers to a phenomenon in which an electrochromic material is reversibly colored or discolored by an oxidation or reduction reaction of the electrochromic material. Electrochromic devices may include materials that receive electrons (ie, through a reduction reaction) or lose electrons (ie, through an oxidation reaction) that color or decolorize. The electrochromic device can be driven at a low driving voltage, and the amount of transmitted light can be controlled by controlling the driving voltage.

Electrochromic devices are being used in smart windows for construction and electrochromic mirrors for automobiles.

The technical problem to be achieved by the present invention is to manufacture an excellent linear electrochromic device through a simple manufacturing process.

The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A method for manufacturing a linear electrochromic device according to the present invention includes a first substrate, a first electrode layer on the first substrate, a second electrode layer on the first electrode layer, an electrolyte layer interposed between the first electrode layer and the second electrode layer, and Forming a plate-shaped electrochromic element including an electrochromic layer, and cutting the plate-shaped electrochromic element in a direction perpendicular to a top surface of the first substrate to form a linear electrochromic structure pattern and forming a protective layer covering at least a portion of the linear electrochromic structure pattern.

According to some embodiments, cutting the plate-shaped electrochromic device may include laser cutting, sawing, cutting, or slitting.

According to some embodiments, cutting the plate-shaped electrochromic device may not include an etching process.

According to some embodiments, the plate-shaped electrochromic device further includes a second substrate on the second electrode layer, and an ion storage layer between the second electrode layer and the electrolyte layer, and forming the plate-shaped electrochromic device includes a first forming a plate-shaped structure, forming a second plate-shaped structure, and bonding the first plate-shaped structure and the second plate-shaped structure, wherein forming the first plate-shaped structure is performed on the first substrate Including sequentially forming the first electrode layer, the electrochromic layer, and the electrolyte layer, and forming the second plate-shaped structure by sequentially forming the second electrode layer and the ion storage layer on the second substrate Including forming, the electrolyte layer and the ion storage layer may be in contact.

In some embodiments, the electrochromic layer covers a portion of the upper surface of the first electrode layer, the electrolyte layer covers the upper surface of the electrochromic layer, and one edge of the first electrode layer includes the electrochromic layer and the exposed by the electrolyte layer, the ion storage layer may cover a portion of an upper surface of the second electrode layer, and one edge of the second electrode layer may be exposed by the ion storage layer.

According to some embodiments, coupling the first plate-shaped structure and the second plate-shaped structure is a plan view, wherein one edge of the exposed first electrode layer and one edge of the exposed second electrode layer are spaced apart from each other may include

In some embodiments, the linear electrochromic structure pattern may include a first support pattern, a first electrode pattern on the first support pattern, a second electrode pattern on the first electrode pattern, the first electrode pattern, and the second an electrochromic pattern between the electrode patterns, and an electrolyte pattern, wherein the protective layer may cover side surfaces of the electrochromic pattern and the electrolyte pattern.

In some embodiments, the first electrode pattern and the second electrode pattern may be exposed by the passivation layer, and the exposed portion of the first electrode pattern and the exposed portion of the second electrode pattern may be spaced apart from each other.

According to some embodiments, the linear electrochromic structure pattern may have a long side and a short side in a plan view, and a length of the long side may be 10 times or more and 100,000 times or less than a length of the short side.

According to some embodiments, the width of the short side may be 10 mm to 300 mm.

According to some embodiments, the long side may be a straight line or a curved line.

According to some embodiments, forming the plate-shaped electrochromic structure includes sequentially forming the first electrode layer, the electrochromic layer, the electrolyte layer, and the second electrode layer on the first substrate,

One edge of the first electrode layer may be exposed by the electrochromic layer, the electrolyte layer, and the second electrode layer.

According to some embodiments, forming the plate-shaped electrochromic structure further includes forming a protective film covering a portion of an upper surface of the second electrode layer, wherein one edge of the second electrode layer is exposed by the protective film, In a plan view, the exposed portion of the second electrode layer may be spaced apart from the exposed portion of the first electrode layer.

According to some embodiments, the protective layer is PI (polyimide), PMMA (poly methyl methacrylate), PDMS (polydimethylsiloxane), Silicon, Siloxane, PVC (polyvinyl chloride), PE (polyethylene), Teflon (Teflon), silicon rubber ( silicone rubber), PUT (polyurethane), PP (polypropylene), PIB (polyisobutylene), PO (polyolefin), PC (polycarbonate), PS (polystyrene), PTFE (polytetrafluoroethylene), FEP (fluorinated ethylene propylene), ABS (acrylonitrile butadiene) styrene), PPP (polyphenylene polymer), resin, nylon, PEG, PVB, PVA, PEO, PPO, PAN, PVDF, may include at least one of PVDF-HFP.

According to some embodiments, the first substrate may include at least one of plastic, polymer, fiber, fabric, and cellulose.

According to some embodiments, forming a plurality of linear electrochromic structure patterns on a substrate, wherein the linear electrochromic structure patterns are spaced apart from each other in a first direction parallel to an upper surface of the substrate, the substrate, the linear forming a protective layer covering the electrochromic structure patterns and filling between the linear electrochromic structure patterns, and cutting the protective layer between the adjacent linear electrochromic structure patterns in a direction perpendicular to the upper surface of the substrate may include

According to some embodiments, each of the linear electrochromic structure patterns includes a first electrode pattern, a second electrode pattern spaced apart from the first electrode pattern, an electrolyte pattern between the first electrode pattern and the second electrode, and It may include an electrochromic pattern.

In some embodiments, the forming of the linear electrochromic structure patterns includes forming the first electrode patterns along the first direction on the substrate, and electrolyte patterns overlapping each of the first electrode patterns. , and sequentially forming electrochromic patterns and second electrode patterns, wherein the electrolyte pattern may expose one edge of the first electrode pattern.

According to some embodiments, each of the linear electrochromic structure patterns may have a long side and a short side in a plan view, and a length of the long side may be 10 times or more and 100,000 times or less than the length of the short side.

According to some embodiments, the width of the short side may be 10 mm to 300 mm.

Through the manufacturing method of the linear electrochromic device according to the present invention, it is possible to simply manufacture an excellent linear electrochromic device.

1A, 2A, 3A, 4A, 5A, and 6A are plan views schematically illustrating a manufacturing process of an electrochromic device according to an embodiment of the present invention.
1B, 2B, 3B, 4B, 5B, and 6B are cross-sectional views taken along II′ and II-II′ of FIGS. 1A, 2A, 3A, 4A, 5A, and 6A, respectively.
7A, 8A, 9A, and 10A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments.
7B, 8B, 9B, and 10B are cross-sectional views taken along II' and II-II' of some of FIGS. 7A, 8A, and 9A and 10B.
11A, 12A, 13A, 14A, and 15A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments.
11B, 12B, 13B, 14B and 15B are cross-sectional views taken along II′ and II-II′ of FIGS. 11A, 12A, 13A, 14A and 15A.
16, 17A, 18A, 19A, 20A, and 21A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments.
17B, 18B, 19B, 20B, and 21B are cross-sectional views taken along II′ and II-II′ of FIGS. 17A, 18A, 19A, 20A, and 21A.
22, 23A, 24A, 25A, 26A, and 27A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments.
23B, 24B, 25B, 26B, and 27B are cross-sectional views taken along II′ and II-II′ of FIGS. 23A, 24A, 25A, 26A and 27A.
28 is a diagram illustrating linear electrochromic devices manufactured according to some embodiments.
29 is a diagram illustrating a linear electrochromic device manufactured according to some embodiments.

In order to fully understand the configuration and effect of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, and may be embodied in various forms and various modifications may be made. However, it is provided so that the disclosure of the present invention is complete through the description of the present embodiments, and to fully inform those of ordinary skill in the art to which the present invention belongs, the scope of the invention. In the accompanying drawings, for convenience of description, the size is enlarged than the actual size, and the ratio of each component may be exaggerated or reduced.

Unless otherwise defined, terms used in the embodiments of the present invention may be interpreted as meanings commonly known to those of ordinary skill in the art. Hereinafter, the present invention will be described in detail by describing exemplary embodiments of the present invention with reference to the accompanying drawings.

Hereinafter, in this specification, the first direction D1 refers to a direction parallel to the upper surface of the substrate 100L or the first substrate 100L, which will be described later. The second direction D2 is parallel to the substrate 100L or the upper surface of the first substrate 100L and is perpendicular to the first direction D1 . The third direction D3 refers to a direction perpendicular to the upper surface of the substrate 100L or the first substrate 100L.

<Example 1>

1A, 2A, 3A, 4A, 5A, and 6A are plan views schematically illustrating a manufacturing process of a linear electrochromic device according to an embodiment of the present invention. 1B, 2B, 3B, 4B, 5B, and 6B are cross-sectional views taken along lines II' and II-II' of FIGS. 1A, 2A, 3A, 4A, 5A, and 6A, respectively.

1A and 1B , a first plate-shaped structure P1 including a first substrate 100L, a first electrode layer 200L, an electrochromic layer 300L, and an electrolyte layer 400L may be formed. . The first plate-shaped structure P1 may be formed by sequentially stacking the first electrode layer 200L, the electrochromic layer 300L, and the electrolyte layer 400L on the first substrate 100L.

The first substrate 100L may be in the form of a film having a small thickness compared to the area of the upper surface of the first substrate 100L. The first substrate 100L may include a material having good flexibility. The first substrate 100L may include any one of plastic, polymer, glass, fiber, fabric, and cellulose. Specifically, the first substrate 100L is polyethylene glycol (PEG (poly(ethylene glycol), PEG), polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), polyolefin (PO), polyvinyl alcohol ( PVA), polyurethane (PU), nylon, polycarbonate (PC), polyester, polyacrylonitrile (PAN), polyacetal (POM), polytetrafluoroethylene (PTFE), fluorinated ethylene Propylene (fluorinated ethylene propylene, FEP), cyclic polyolefin (COP), modified PPO (MPPO), polyethylene terephthalate (PET), polycarbonate (Polycabonate, PC), acrylonitrile-butadiene-styrene Resin (acrylonitrile-butadiene-styrene copolymer, ABS), polymethyl methacrylate (PMMA), polyethylene naphthalate (PEN), polyether sulfone (PES), cyclic olefin polymer (Cyclic) Olefin Copolymer, COC), TAC (Triacetylcellulose) film, polyvinyl alcohol (Polyvinyl alcohol, PVA) film, fabric, cellulose, polyimide (Polyimide, PI) film, may include at least one of polystyrene (PS) have.

A first electrode layer 200L may be formed on the first substrate 100L. The thickness of the first electrode layer 200L may be 0.1 nm to 10 μm. The first electrode layer 200L may be transparent or translucent.

The first electrode layer 200L may be formed of one layer or a plurality of stacked layers. The first electrode layer 200L may include a conductive material. Conductive materials include indium zinc oxide (IZO), indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), and tungsten. Doped zinc oxide (WZO), tungsten doped tin oxide (WTO), gallium doped zinc oxide (GZO), antimony doped tin oxide (ATO), indium doped zinc oxide (IZO), niobium (Nb) doped titanium oxide (TiOx), single or multiple oxide-metal-oxide (OMO, oxide-metal-oxide), conductive polymer, conductive organic molecule, carbon nanotube, carbon electrode, graphene, silver nanowire, At least one of aluminum, silver, ruthenium, gold, platinum, tin, chromium, indium, zinc, copper, rubidium, nickel, ruthenium oxide, rubidium oxide, tin oxide, indium oxide, zinc oxide, chromium oxide and molybdenum can

An electrochromic layer 300L may be formed on the first electrode layer 200L. The electrochromic layer 300L may cover a portion of the upper surface of the first electrode layer 200L. For example, the electrochromic layer 300L may be formed to expose one edge of the first electrode layer 200L.

The electrochromic layer 300L may include an electrochromic material. The electrochromic material may include an oxidizing electrochromic material or a reducing electrochromic material. The oxidation electrochromic material may include at least one of Prussian blue, nickel oxide (NiO), iridium oxide (IrO2), metal oxides, phenothiazine or phenothiazine derivatives, vanadium oxide (V2O5), triphenylamine or triphenylamine derivatives. The reduction electrochromic material may _{include at least one of tungsten oxide (WO 3)} , metal oxides, metal hydrides, polyaniline, and viologen series. In some other embodiments, an ion storage layer may be formed instead of the electrochromic layer 300L. The ion storage layer will be described later.

An electrolyte layer 400L may be formed on the electrochromic layer 300L. The electrolyte layer 400L may be in contact with the electrochromic layer 300L and may not be in contact with the first electrode layer 200L. One exposed edge of the first electrode layer 200L may be exposed by the electrochromic layer 300L and the electrolyte layer 400L. The electrolyte layer 400L may provide electrolyte ions involved in the discoloration reaction. The electrolyte layer 400L may include a polymer, an organic molecule, an ionic liquid, a solvent, and an ionic molecular sieve.

Polymers include PEG (poly(ethylene glycol)), PMMA (Poly methyl methacrylate), PBA (Poly butyl Acrylate), PVB (Poly Vinyl Butyrate), PVA (Polyvinyl Alcohol), PEO (poly(ethylene oxide)), PPO (poly (propylene oxide)), PAN (poly acrylonitrile), PVDF (poly (vinylidene fluoride)), and PVDF-HFP (poly (vinylidene fluoride-co-hexafluoropropylene)), may include at least one of a block copolymer have.

The organic molecule, solvent, or ionic liquid is propylene carbonate (PC), butylene carbonate (BC), ethylene carbonate (EC), gamma-butyloactone (gamma-BL), gamma-VL, NMO, dimethyl carbonate ( DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylmethyl carbonate (PMC), ethyl acetate (EA), ethylene blue (EB), water (water, HO), and methylene blue (MB), It may include at least one of morpholinium, imidazolium, quaternary ammonium, quaternary phosphonium, Br ^- , Cl ^- , NO ₃ ^- , BF ₄ ^- , PF ₆ ^-.

The ionic molecular sieve may include at least one of a lithium ion product and a hydrogen ion product.

Lithium ion products are lithium perchlorate (LiClO ₄ ), LiBF ₄ , LiPF ₆ , LiAsF ₆ , LiTf (lithium triflate, LiCF ₃ SO ₃ ), LiIm (lithium Imdide, Li[N(SO ₂ CF ₃ ) ₂ ]), LiBeTi It may include at least one of (Li[N(SO ₂ CF ₂ CF ₃ ) ₂ ]), LiBr, and LiI.

The hydrogen ion product is at least one of hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), phosphoric acid (H ₃ PO ₄ ), acetic acid (CH ₃ COOH), perchloric acid (HClO ₄ ), and formic acid (HCOOH) may contain one.

2A and 2B , a second plate-shaped structure P2 including a second substrate 700L, a second electrode layer 600L, and an ion storage layer 500L may be formed. The second plate-shaped structure may be formed by sequentially stacking the second electrode layer 600L and the ion storage layer 500L on the second substrate 700L.

The second substrate 700L may be substantially the same as the first substrate 100L. The second electrode layer 600L may include substantially the same material as the first electrode layer 200L.

An ion storage layer 500L may be formed on the second electrode layer 600L. The ion storage layer 500L may cover a portion of the upper surface of the second electrode layer 600L. For example, the ion storage layer 500L may be formed such that one edge of the second electrode layer 600L is exposed.

The ion storage layer 500L is a layer formed to balance charge with the electrochromic layer 300L during a reversible oxidation/reduction reaction for discoloration of the electrochromic material included in the electrochromic layer 300L. can mean

The ion storage layer 500L may include an electrochromic material having a color change characteristic complementary to that of the electrochromic material included in the electrochromic layer 300L. For example, when the electrochromic layer 300L includes a reducing color change material, the ion storage layer 500L may include an oxidative electrochromic material. Alternatively, when the electrochromic layer 300L includes an oxidative color change material, the ion storage layer 500L may include a reducing electrochromic material.

Referring to FIGS. 3A and 3B , the first plate-shaped structure P1 of FIGS. 1A and 1B and the second plate-shaped structure P2 of FIGS. 2A and 2B are combined to form a plate-shaped electrochromic device PT. have. The plate-shaped electrochromic element PT may be an electrochromic element having a planar, large area. Here, the large area may mean a larger area compared to that manufactured for research purposes.

The second plate-shaped structure P2 may be attached on the first plate-shaped structure P1 , and the first substrate 100L and the second substrate 700L may be formed to be spaced apart from each other in the third direction D3 . . A first electrode layer 200L, an electrochromic layer 300L, an electrolyte layer 400L, an ion storage layer 500L, and a second electrode layer 600L are interposed between the first substrate 100L and the second substrate 700L. may be interposed.

In a plan view, the exposed edge of the first electrode layer 200L and the exposed edge of the second electrode layer 600L may not overlap each other. In a plan view, the exposed edge of the first electrode layer 200L and the exposed edge of the second electrode layer 600L may be spaced apart from each other in the first direction D1 .

Referring to FIGS. 4A, 4B, 5A, and 5B, a cutting process (CT) is performed from one surface 700T of the second substrate 700L toward one surface 100B of the first substrate 100L. can The cutting process (CT) may refer to an etching process such as laser cutting, sawing, simple cutting, or slitting, or separation by pure physical force rather than chemical action.

The cutting process CT may be performed along the third direction D3 . Specifically, the cutting process CT may be performed in a direction perpendicular to the upper and/or lower surfaces of the first substrate 100L and the second substrate 700L. The second substrate 700L, the second electrode layer 600L, the ion storage layer 500L, the electrolyte layer 400L, the electrochromic layer 300L, the first electrode layer 200L, and the first substrate 100L are sequentially cut. can be

The cutting process CT may be performed along the plurality of cutting lines CL. Each of the cutting lines CL may correspond to a line parallel to the upper surface of the plate-shaped electrochromic element PT and crossing the upper surface of the plate-shaped electrochromic element PT. A plurality of linear electrochromic structure patterns LP may be formed by a plurality of cutting processes CT. Each of the linear electrochromic structure patterns LP includes a first support pattern 100P, a first electrode pattern 200P, an electrochromic pattern 300P, an electrolyte pattern 400P, and an ion storage pattern 500P, which are sequentially stacked. , a second electrode pattern 600P, and a second support pattern 700P.

In a plan view, a width W1 between adjacent cut lines CL may correspond to a width of a short side of the linear electrochromic structure pattern LP. In a plan view, a length W2 of each of the cutting lines CL may correspond to a width of a long side of the linear electrochromic structure pattern LP. A ratio of the width W1 of the short side and the width W2 of the long side of the linear electrochromic structure pattern LP may be 1:10 to 1:100,000. The width W1 of the short side may be 10 mm to 300 mm.

In a plan view, the side surfaces of the cut lines CL and the linear electrochromic structure pattern LP may have a straight line or a curved shape.

6A and 6B , the protective layer PL surrounding the linear electrochromic structure pattern LP is formed, thereby forming a linear electrochromic device. The linear electrochromic device may include a linear electrochromic structure pattern LP and a passivation layer PL.

The passivation layer PL may be coated to cover the remaining portion of the linear electrochromic device except for the exposed portion of the first electrode pattern 200P and the exposed portion of the second electrode pattern 600P. The passivation layer PL may be formed on the remaining portions except for both ends of the linear electrochromic structure pattern LP. The side surfaces of the electrode patterns 200P and 600P, the electrochromic pattern 300P, the electrolyte pattern 400P, and the ion storage pattern 500P may be protected by the protective layer PL. The exposed side and/or the cut surface of the linear electrochromic structure pattern LP may be protected from external oxygen or water vapor by the passivation layer PL. The stability of the linear electrochromic structure pattern LE may be increased from an external impact or environment by the protective layer PL. In addition, the linear electrochromic element can have good flexibility by the protective film PL.

The protective layer PL may be formed by coating and drying a low-viscosity polymer material having fluidity. The coating method of the polymer material may be performed by at least one of drop casting, spin coating, dip coating, spray coating, compression, and extrusion. The drying process may be performed by at least one of natural drying, heat treatment, or drying according to light of uv/vis/IR wavelength.

Polymer materials include PI (polyimide), PMMA (poly methyl methacrylate), PDMS (polydimethylsiloxane), Silicon, Siloxane, PVC (polyvinyl chloride), PE (polyethylene), Teflon (Teflon), silicon rubber, PUT (polyurethane) ), PP (polypropylene), PIB (polyisobutylene), PO (polyolefin), PC (polycarbonate), PS (polystyrene), PTFE (polytetrafluoroethylene), FEP (fluorinated ethylene propylene), ABS (acrylonitrile butadiene styrene), PPP (polyphenylene polymer) ), resin, nylon, PEG, PVB, PVA, PEO, PPO, PAN, PVDF, and PVDF-HFP, fiber, fabric, and may include at least one of cellulose.

According to some embodiments, the first electrode pattern 200P and/or the second electrode pattern 600P may not be exposed by the passivation layer PL. In this case, the first electrode pattern 200P and/or the second electrode pattern 600P may be exposed by additionally removing some patterns of the passivation layer PL and the linear electrochromic structure pattern LP.

<Example 2>

7A, 8A, 9A, and 10A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments. 7B, 8B, 9B, and 10B are cross-sectional views taken along lines II' and II-II' of some of FIGS. 7A, 8A, and 9A and 10B.

Except for those described below, since it has been described in detail through the first embodiment, a description of the components using the same reference numerals will be omitted.

7A and 7B , a plurality of linear electrochromic structure patterns LP may be formed on the substrate 100L. Each of the linear electrochromic structure patterns LP may extend along the first direction D1 , and the linear electrochromic structure patterns LP may be spaced apart from each other along the second direction D2 .

Each of the linear electrochromic structure patterns LP includes a first electrode pattern 200P, an electrochromic pattern 300P, an electrolyte pattern 400P, and an ion storage pattern 500P sequentially stacked in a direction perpendicular to the substrate 100L. ), and a second electrode pattern 600P.

First, first electrode patterns 200P spaced apart along the first direction D1 may be formed on the substrate 100L. Electrochromic patterns 300P covering a portion of the upper surfaces of the first electrode patterns 200P may be formed. The electrochromic patterns 300P may expose one edge of the first electrode patterns 200P.

Electrolyte patterns 400P, ion storage patterns 500P, and second electrode patterns 600P may be sequentially formed on each of the electrochromic patterns 300P. The edge of the first electrode pattern 200P may be exposed by the electrochromic pattern 300P, the electrolyte pattern 400P, the ion storage pattern 500P, and the second electrode pattern 600P.

The first electrode patterns 200P, the electrochromic patterns 300P, the electrolyte patterns 400P, the ion storage patterns 500P, and the second electrode patterns 600P are, for example, sputtering processes or using a mask. It may be formed by a deposition process.

In some embodiments, the formation order of the electrochromic pattern 300P and the ion storage pattern 500P may be changed. In some other embodiments, the electrochromic pattern 300P may be formed instead of the ion storage pattern 500P.

8A and 8B , a protective material layer PM covering the upper surface of the substrate 100L and the linear electrochromic structure patterns LP may be formed. The protective material layer PM covers a portion of the top surface and a portion of both sides of each of the linear electrochromic structure patterns LP, and fills a part of a gap between the linear electrochromic structure patterns LP. can

Specifically, the protective material layer PM may not cover the exposed portion of the first electrode pattern 200P, or may cover only a portion of the first electrode pattern 200P. The protective material layer PM may cover a portion of the second electrode pattern 600P. That is, a portion of the upper surface of the first electrode pattern 200P and a portion of the upper surface of the second electrode pattern 600P may be exposed by the protective material layer PM. In a plan view, a portion of the exposed first electrode pattern 200P and a portion of the exposed second electrode pattern 600P may be spaced apart from each other in the first direction D1 . The protective material layer PM may be formed by coating and drying a low-viscosity polymer material having fluidity.

The coating method of the polymer material may be performed by at least one of drop casting, spin coating, dip coating, spray coating, compression, and extrusion. The drying process may be performed by at least one of natural drying, heat treatment, or drying according to light of uv/vis/IR wavelength.

Polymer materials include PI (polyimide), PMMA (poly methyl methacrylate), PDMS (polydimethylsiloxane), Silicon, Siloxane, PVC (polyvinyl chloride), PE (polyethylene), Teflon (Teflon), silicon rubber, PUT (polyurethane) ), PP (polypropylene), PIB (polyisobutylene), PO (polyolefin), PC (polycarbonate), PS (polystyrene), PTFE (polytetrafluoroethylene), FEP (fluorinated ethylene propylene), ABS (acrylonitrile butadiene styrene), PPP (polyphenylene polymer) ), resin, nylon, PEG, PVB, PVA, PEO, PPO, PAN, PVDF, and may include at least one PVDF-HFP.

Referring to FIGS. 9A, 9B, 10A and 10B , between the adjacent linear electrochromic structure patterns LP, along the third direction D3, from the top surface of the protective material layer PM to the substrate 100L. The cutting process (CT) may proceed to the lower surface.

A linear electrochromic device may be formed by a cutting process (CT). The linear electrochromic device may include a linear electrochromic structure pattern LP, a passivation layer PL, and a support pattern 100P. The support pattern 100P and the protective layer PL may be respectively formed by the cutting process of the substrate 100 and the protective material layer PM.

According to some embodiments, the first electrode pattern 200P and/or the second electrode pattern 600P may not be exposed by the passivation layer PL. In this case, the first electrode pattern 200P and/or the second electrode pattern 600P may be exposed by additionally removing some patterns of the passivation layer PL and the linear electrochromic structure pattern LP.

<Example 3>

11A, 12A, 13A, 14A, and 15A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments. 11B, 12B, 13B, 14B and 15B are cross-sectional views taken along lines II' and II-II' of FIGS. 11A, 12A, 13A, 14A and 15A.

Except for those described below, since it has been described in detail through the first embodiment, a description of the components using the same reference numerals will be omitted.

11A and 11B , the first electrode layer 200L may be formed on the substrate 100L. The electrochromic layer 300L may cover a portion of the upper surface of the first electrode layer 200L. For example, the electrochromic layer 300L may be formed to expose one edge of the first electrode layer 200L. An electrolyte layer 400L, an ion storage layer 500L, and a second electrode layer 600L may be sequentially formed on the electrochromic layer 300L. One edge of the first electrode layer 200L may be exposed by the electrochromic layer 300L, the electrolyte layer 400L, the ion storage layer 500L, and the second electrode layer 600L.

12A and 12B , the protective material layer PM covering a portion of the second electrode layer 600L is formed, thereby forming a plate-shaped electrochromic device PT. The plate-shaped electrochromic device PT includes a substrate 100L, a first electrode layer 200L, an electrochromic layer 300L, an electrolyte layer 400L, an ion storage layer 500L, and a second electrode layer 600L and a protective material. It may include a layer (PM).

13A, 13B, 14A, and 14B , a cutting process CT may be performed from the one surface PMT of the protective material layer PM toward the one surface 100B of the substrate 100L. The protective material layer (PM), the second electrode layer (600L), the ion storage layer (500L), the electrolyte layer (400L), the electrochromic layer (300L), the first electrode layer (200L) and the substrate (100L) can be cut in sequence. have. A plurality of linear electrochromic structure patterns LP may be formed by the cutting process CT. Each of the linear electrochromic structure patterns LP includes a first support pattern 100P, a first electrode pattern 200P, an electrochromic pattern 300P, an electrolyte pattern 400P, an ion storage pattern 500P, which are sequentially stacked. It may include a second electrode pattern 600P and a second support pattern PP.

15A and 15B , a passivation layer PL covering the linear electrochromic structure pattern LP may be formed. The passivation layer PL may be coated to cover the remaining portions except for the exposed portion of the first electrode pattern 200P and the exposed portion of the second electrode pattern 600P. The passivation layer PL may be formed on the remaining portions except for both ends of the linear electrochromic structure pattern LP. Sides of the electrochromic pattern 300P, the electrolyte pattern 400P, and the ion storage pattern 500P may be protected by the protective layer PL. The protective layer PL may be formed by coating and drying a low-viscosity polymer material having fluidity. The passivation layer PL may include substantially the same material as the second support pattern PP.

The protective layer PL may be formed by coating and drying a low-viscosity polymer material having fluidity. The coating method of the polymer material may be performed by at least one of drop casting, spin coating, dip coating, spray coating, compression, and extrusion. The drying process may be performed by at least one of natural drying, heat treatment, or drying according to light of uv/vis/IR wavelength.

According to some embodiments, the first electrode pattern 200P and/or the second electrode pattern 600P may not be exposed by the passivation layer PL. In this case, the first electrode pattern 200P and/or the second electrode pattern 600P may be exposed by additionally removing some patterns of the second protective layer PL2 and the linear electrochromic structure pattern LP.

16, 17A, 18A, 19A, and 20A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments. 17B, 18B, 19B, and 20B are cross-sectional views taken along lines II' and II-II' of FIGS. 17A, 18A, 19A, and 20A. 21 is a cross-sectional view corresponding to I-I' and II-II' of FIG. 20A.

The first plate-shaped electrochromic element PT1 of FIG. 16 shows the planar shape of the plate-shaped electrochromic element PT of FIGS. 3A and 3B . 16, 17A, and 17B , the first plate-shaped electrochromic device PT1 may be cut along the cutting line CL so that only one of the exposed electrode layers 200L and 600L is exposed. The first plate-shaped electrochromic element PT1 may be cut to form a second plate-shaped electrochromic element PT2 having a smaller planar area. In the second plate-shaped electrochromic element PT2, along the first direction D1, the upper surface of the first electrode layer 200L of the second plate-shaped electrochromic element PT2 is exposed, and the upper surface of the second electrode layer 600L is may not be exposed. In another embodiment, along the first direction D1 of the second plate-shaped electrochromic element PT2, the upper surface of the first electrode layer 200L of the second plate-shaped electrochromic element PT2 is not exposed, and the second electrode layer (600L) can be cut to expose the upper surface.

18A, 18B, 19A, and 19B , a cutting process CT is performed from one surface 700T of the second substrate 700L toward one surface 100B of the first substrate 100L. can A plurality of linear electrochromic structure patterns LP may be formed by a cutting process CT along the plurality of cutting lines CL.

Referring to FIGS. 20A and 20B , the protective layer PL surrounding the linear electrochromic structure pattern LP is formed to form a linear electrochromic device. The linear electrochromic device may include a linear electrochromic structure pattern LP and a passivation layer PL. The passivation layer PL may be coated to cover the remaining portions except for both ends E1 and E2 of the linear electrochromic structure pattern LP. A portion of the upper surface of the first electrode pattern 200P located at one end E1 of the linear electrochromic structure pattern LP may be exposed by the passivation layer PL. A voltage may be applied to the exposed first electrode pattern 200P by serving as an electrode. In contrast, since the second electrode pattern 600P located at the other end E2 of the linear electrochromic structure pattern LP is not exposed, it may be difficult to apply a voltage.

20A and 21 , a process of removing some of the patterns located at the other end E2 of the linear electrochromic structure pattern LP may be performed. For example, the first support pattern 100P, the first electrode pattern 200P, the electrochromic pattern 300P, and the electrolyte positioned at the other end E2 of the linear electrochromic structure pattern LP not surrounded by the protective film PL. The pattern 400P may be removed. Accordingly, a portion of one surface of the ion storage pattern 500P may be exposed. The exposed ion storage pattern 500P may be coated with a conductive material such as silver (Ag) paste or copper (Cu) tape, and then may be connected to an external terminal. The exposed ion storage pattern 500P is electrically connected to the second electrode pattern 600P, and may serve as a passage for electricity to which a voltage is applied. In some embodiments, even the ion storage pattern 500P may be removed to expose a portion of one surface of the second electrode pattern 600P.

22, 23A, 24A, 25A, 26A, and 27A are plan views schematically illustrating a manufacturing process of an electrochromic device according to some embodiments. 23B, 24B, 25B, 26B, and 27B are cross-sectional views taken along lines II' and II-II' of FIGS. 23A, 24A, 25A, 26A and 27A.

The first plate-shaped electrochromic element PT1 of FIG. 22 shows the planar shape of the plate-shaped electrochromic element PT of FIGS. 3A and 3B . 22, 23A, and 23B , the first plate-shaped electrochromic element PT1 may be cut to become a second plate-shaped electrochromic element PT2 having a small planar area. To be cut along at least one cutting line CL so that the upper surfaces of each of the exposed electrode layers 200L and 600L of the first plate-shaped electrochromic element PT1 are not exposed in the second plate-shaped electrochromic element PT2. can In the first direction D1 , the upper surface of the first electrode layer 200L and the upper surface of the second electrode layer 600L of the second plate-shaped electrochromic device PT2 may not be exposed.

24A, 24B, 25A, and 25B , linear electrochromic structure patterns LP may be formed by a cutting process CT along a plurality of cutting lines CL.

26A and 26B , the protective layer PL surrounding the linear electrochromic structure pattern LP is formed, thereby forming a linear electrochromic device. The passivation layer PL may be coated to cover both ends E1 and E2 of the linear electrochromic structure pattern LP, or to cover the remaining portions except the same. An upper surface of the first electrode pattern 200P and an upper surface of the second electrode pattern 600P of the linear electrochromic pattern structure pattern LP may be in an unexposed state.

27A and 27B , a process of removing some of the patterns located at both ends E1 and E2 of the linear electrochromic structure pattern LP may be performed. A second support pattern 700P, a second electrode pattern 600P, an ion storage pattern 500P, and an electrolyte pattern positioned at one end E1 of the linear electrochromic structure pattern LP not surrounded by the protective film PL (400P) can be removed. Accordingly, a portion of one surface of the electrochromic pattern 300P of the one end E1 of the linear electrochromic structure pattern LP may be exposed. The exposed ion storage pattern 500P may be coated with a conductive material such as silver (Ag) paste or copper (Cu) tape, and then may be connected to an external terminal. The exposed electrochromic pattern 300P is electrically connected to the first electrode pattern 200P, and may serve as a passage for electricity to which a voltage is applied. In some embodiments, the electrochromic pattern 300P located at one end E1 of the linear electrochromic structure pattern LP not surrounded by the passivation layer PL is additionally removed and a part of one surface of the first electrode pattern 200P may be exposed.

The first support pattern 100P, the first electrode pattern 200P, the electrochromic pattern 300P, and the electrolyte pattern located at the other end E2 of the linear electrochromic structure pattern LP not surrounded by the protective layer PL. (400P) can be removed. Accordingly, a portion of one surface of the ion storage pattern 500P of the other end E2 of the linear electrochromic structure pattern LP may be exposed. The exposed ion storage pattern 500P may be coated with a conductive material such as silver (Ag) paste or copper (Cu) tape, and then may be connected to an external terminal. The exposed ion storage pattern 500P is electrically connected to the second electrode pattern 600P, and may serve as a passage for electricity to which a voltage is applied. In some embodiments, the ion storage pattern 500P located at the other end E2 of the linear electrochromic structure pattern LP not surrounded by the protective layer PL is additionally removed, and a part of one surface of the second electrode pattern 600P is removed. may be exposed.

<Experimental example>

A plurality of linear electrochromic devices coated with a protective member according to Example 1 were formed. The specific order is as follows. To form the first plate-shaped structure, an ITO PET film having a sheet resistance of 30 ohm/sq was prepared as a substrate. A low-viscosity Prussian blue (PB) particle solution was coated on the ITO film. A dried Prussian blue (PB) layer was formed through the heat treatment process.

The electrolyte was coated on Prussian blue (PB) in a dried state. The electrolyte was a material containing PVB polymer, and was coated using a blade bar. Specifically, a polymer gel electrolyte (Adcro Co., Ltd., Busan, Korea) was used as the electrolyte, and the polymer gel electrolyte was coated to a thickness of 200 μm before drying. At 80 degrees, the thickness after drying for 1 minute was measured to be about 50 mm. The viscosity of the polymer gel electrolyte was about 2500p, and the ionic conductivity was 0.2Scm-.

In order to form the second plate-shaped structure, an ITO PET film having a sheet resistance of 30 ohm/sq was prepared as a substrate. A low-viscosity WO- ₃ particle solution was coated on an ITO PET film _{to form a WO 3} thin film, a reductive discoloration material, and dried through a heat treatment process.

The first plate-shaped structure and the second plate-shaped structure were laminated (merged) so that the electrolyte of the first plate-shaped structure and the WO _{3 thin film of the second plate-shaped structure could be bonded.} Then, a linear electrochromic structure pattern was formed through a cutting process. The linear electrochromic pattern was coated with a PDMS polymer to form a linear electrochromic device. 28 is a view showing electrochromic devices manufactured according to the above experimental example. The bleached state (A) and the colored state (B) are shown. In the decolored state (A), a voltage of 2V was applied to the linear electrochromic element, and in the colored state (B), a voltage of -2V was applied to the linear electrochromic element.

29 shows a linear electrochromic device fabricated in accordance with some embodiments. Referring to FIG. 29 , the linear electrochromic device according to the present invention is flexible and can be bent or bent.

The method for manufacturing a linear electrochromic device according to the present invention is to undergo a cutting process after forming a large-area electrochromic device, so that it can be manufactured without going through a complicated process, and the linear electrochromic device is manufactured by forming a protective film covering the cut surface. can protect

As mentioned above, although embodiments of the present invention have been described with reference to the accompanying drawings, those of ordinary skill in the art to which the present invention pertains can practice the present invention in other specific forms without changing its technical spirit or essential features. You will understand that there is Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

100L: first substrate
200L: first electrode layer
300L: electrochromic layer
400L: electrolyte layer
500L: ion storage layer
600L: second electrode layer
700L: second substrate
CL: cutting line
CT: Cutting process
PL: Shield

Claims (20)

A plate shape electricity comprising a first substrate, a first electrode layer on the first substrate, a second electrode layer on the first electrode layer, an electrolyte layer interposed between the first electrode layer and the second electrode layer, and an electrochromic layer forming a color-changing element;
forming a linear shape electrochromic structure pattern by cutting the plate-shaped electrochromic device in a direction perpendicular to an upper surface of the first substrate; and
and forming a protective layer covering at least a portion of the linear electrochromic structure pattern.
According to claim 1,
Cutting the plate-shaped electrochromic device comprises:
A method of manufacturing an electrochromic device comprising laser cutting, sawing, simple cutting, or slitting.
3. The method of claim 2,
Cutting the plate-shaped electrochromic device comprises:
A method of manufacturing an electrochromic device that does not include an etching process.
According to claim 1,
The plate-shaped electrochromic device further includes a second substrate on the second electrode layer, and an ion storage layer between the second electrode layer and the electrolyte layer,
Forming the plate-shaped electrochromic device comprises:
forming a first plate-shaped structure;
forming a second plate-shaped structure; and
Comprising combining the first plate-shaped structure and the second plate-shaped structure,
Forming the first plate-shaped structure comprises:
and sequentially forming the first electrode layer, the electrochromic layer, and the electrolyte layer on the first substrate
Forming the second plate-shaped structure includes sequentially forming the second electrode layer and the ion storage layer on the second substrate in order,
The electrolyte layer and the ion storage layer are in contact with the manufacturing method of the electrochromic device.
5. The method of claim 4,
The electrochromic layer covers a portion of the upper surface of the first electrode layer,
The electrolyte layer covers an upper surface of the electrochromic layer,
One edge of the first electrode layer is exposed by the electrochromic layer and the electrolyte layer,
The ion storage layer covers a portion of the upper surface of the second electrode layer,
One edge of the second electrode layer is exposed by the ion storage layer manufacturing method of the electrochromic device.
6. The method of claim 5,
Combining the first plate-shaped structure and the second plate-shaped structure includes:
From a flat point of view,
and coupling one edge of the exposed first electrode layer and one edge of the exposed second electrode layer to be spaced apart from each other.
According to claim 1,
The linear electrochromic structure pattern comprises:
a first support pattern;
a first electrode pattern on the first support pattern;
a second electrode pattern on the first electrode pattern;
an electrochromic pattern between the first electrode pattern and the second electrode pattern, and an electrolyte pattern,
The method of manufacturing a linear electrochromic device, wherein the protective layer covers side surfaces of the electrochromic pattern and the electrolyte pattern.
8. The method of claim 7,
The first electrode pattern and the second electrode pattern are exposed by the protective layer,
An exposed portion of the first electrode pattern and an exposed portion of the second electrode pattern are spaced apart from each other.
According to claim 1,
The linear electrochromic structure pattern in a plan view
A method of manufacturing a linear electrochromic device having a long side and a short side, wherein the long side is 10 times or more and 100,000 times or less than the length of the short side.
10. The method of claim 9,
A method of manufacturing a linear electrochromic device, wherein the width of the short side is 10 mm to 300 mm.
10. The method of claim 9,
The method of manufacturing a linear electrochromic device wherein the long side is a straight line or a curve
According to claim 1,
Forming the plate-shaped electrochromic structure comprises:
and sequentially forming the first electrode layer, the electrochromic layer, the electrolyte layer, and the second electrode layer on the first substrate,
One edge of the first electrode layer is exposed by the electrochromic layer, the electrolyte layer, and the second electrode layer.
13. The method of claim 12,
Forming the plate-shaped electrochromic structure comprises:
Further comprising forming a protective film covering a portion of the upper surface of the second electrode layer,
One edge of the second electrode layer is exposed by the protective film,
In a plan view, the exposed portion of the second electrode layer is spaced apart from the exposed portion of the first electrode layer.
According to claim 1,
The protective layer is PI (polyimide), PMMA (poly methyl methacrylate), PDMS (polydimethylsiloxane), Silicon, Siloxane, PVC (polyvinyl chloride), PE (polyethylene), Teflon (Teflon), silicon rubber (silicone rubber), PUT (polyurethane) ), PP (polypropylene), PIB (polyisobutylene), PO (polyolefin), PC (polycarbonate), PS (polystyrene), PTFE (polytetrafluoroethylene), FEP (fluorinated ethylene propylene), ABS (acrylonitrile butadiene styrene), PPP (polyphenylene polymer) ), resin, nylon, PEG, PVB, PVA, PEO, PPO, PAN, PVDF, PVDF-HFP, fabric, manufacturing method of a linear electrochromic device comprising at least one of cellulose.
According to claim 1,
The first substrate is a method of manufacturing a linear electrochromic device comprising at least one of plastic, polymer, fiber, fabric, and cellulose.
forming a plurality of linear electrochromic structure patterns on a substrate, wherein the linear electrochromic structure patterns are spaced apart from each other in a first direction parallel to an upper surface of the substrate;
forming a protective layer covering the substrate and the linear electrochromic structure patterns and filling between the linear electrochromic structure patterns; and
and cutting the protective layer between the adjacent linear electrochromic structure patterns in a direction perpendicular to a top surface of the substrate. 17. The method of claim 16,
Each of the linear electrochromic structure patterns comprises:
A method of manufacturing a linear electrochromic device comprising a first electrode pattern, a second electrode pattern spaced apart from the first electrode pattern, an electrolyte pattern between the first electrode pattern and the second electrode, and an electrochromic pattern.
18. The method of claim 17,
Forming the linear electrochromic structure patterns comprises:
forming the first electrode patterns on the substrate along the first direction;
and sequentially forming electrolyte patterns, electrochromic patterns, and second electrode patterns overlapping each of the first electrode patterns,
The electrolyte pattern is a method of manufacturing a linear electrochromic device exposing one edge of the first electrode pattern.
17. The method of claim 16,
Each of the linear electrochromic structure patterns in a plan view
A method of manufacturing a linear electrochromic device having a long side and a short side, wherein the long side is 10 times or more and 100,000 times or less than the length of the short side.
20. The method of claim 19,
A method of manufacturing a linear electrochromic device, wherein the width of the short side is 10 mm to 300 mm.

Images